EP0238685A1 - Process for the production of moulded polyurethane parts - Google Patents

Process for the production of moulded polyurethane parts Download PDF

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Publication number
EP0238685A1
EP0238685A1 EP86104125A EP86104125A EP0238685A1 EP 0238685 A1 EP0238685 A1 EP 0238685A1 EP 86104125 A EP86104125 A EP 86104125A EP 86104125 A EP86104125 A EP 86104125A EP 0238685 A1 EP0238685 A1 EP 0238685A1
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Prior art keywords
radical
carbon atoms
radicals
alkyl radical
compounds
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EP86104125A
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German (de)
French (fr)
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EP0238685B1 (en
Inventor
Helmut Lammerting
Hans-Joachim Dr. Kollmeier
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Evonik Operations GmbH
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TH Goldschmidt AG
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Priority to DE19853509810 priority Critical patent/DE3509810C1/en
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Priority to EP86104125A priority patent/EP0238685B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2125/00—Compositions for processes using internal mould release agents

Definitions

  • the invention relates to a process for producing molded polyurethane parts by reacting at least one polyol with an organic di- or polyisocyanate in the presence of catalysts and mold release agents with shaping.
  • the invention relates in particular to a process for the production of molded polyurethane parts by the reaction injection molding (RIM) process.
  • RIM reaction injection molding
  • Polyurethane molded parts are widely used as body parts, such as aprons, spoilers, fenders, in the automotive industry. Due to their toughness and abrasion resistance, they are suitable as shoe soles, heels and for many other purposes.
  • the curing of the polyurethanes takes place with simultaneous shaping in closed, heated molds.
  • the reaction injection molding process the so-called RIM process, has become particularly important.
  • release agents can be applied to the inner walls of the molds or added to the reaction batch as internal release agents.
  • the internal release agents can belong to different classes of substances. Metal soaps such as zinc stearate are used as internal release agents. Esters of higher fatty acids, natural or synthetic oils, waxes or silicones are used.
  • the internal release agents should be easy to distribute in the reaction mixture, but in order to be able to act as separators, they have to accumulate on the surface of the molded part.
  • organosilicon block copolymers which, in addition to siloxane blocks, have polyoxyalkylene blocks.
  • the structure of the connections obviously plays an important role in the separation behavior.
  • DE-OS 25 43 638 shows that the compounds of the formula the compounds with the formula should be inferior, where in the formulas II to V the indices x each have an average of 3 to 45, the index y each represents an average of 8 to 198, Me is methyl and the rest (-OR) x is a polyoxyalkylene polymer or a polyoxyalkylene copolymer, where R is composed of ethylene residues or butylene residues or mixtures of ethylene or butylene residues with propylene residues, the amount of ethylene or butylene residues in relation to the amount of propylene residues being chosen such that the ratio of the carbon atoms to the oxygen atoms in the entire block (-OR-) 2.0: 1 to 2.9: 1.
  • Siloxanes with such functional groups are known from US Pat. No. 4,076,695. They contain, as functional groups on hydrocarbon groups, carboxyl groups which in turn are connected to the siloxane skeleton by means of an Si-C or SiOC bond.
  • these release agents with carboxyl groups do not form stable mixtures with the polyols which contain amine and optionally Sn catalysts. The addition of these compounds also extends the gel time of the polyurethane system.
  • the invention is therefore based on the object of finding internal release agents for the production of molded polyurethane parts, in particular using the RIM process, which optimally meet the requirements shown at the outset.
  • R1 is the same or different in the molecule and represents an alkyl radical with 1 to 18 carbon atoms or an aryl radical, but at least 70% of the radicals R1 are methyl radicals
  • R2 is R1 or one of the radicals or -R3O (C2H4O) n (C3H6O) m
  • R7 means in which R3 is a divalent hydrocarbon radical with 2 to 4 carbon atoms, R4, R5 are monovalent hydrocarbon radicals or together form part of a morpholine or piperazine ring
  • R6 is a lower alkyl radical with 1 to 4 carbon atoms and R7 is a hydrogen, acyl or the R6 radical
  • z 1 to 10
  • the radical R 1 is bonded to silicon and is preferably a lower alkyl radical having 1 to 4 carbon atoms, particularly preferably the methyl radical.
  • the meaning of the radical R1 can vary in the average molecule, but the condition must be fulfilled that at least 70% of the radicals R1 are methyl radicals.
  • the remaining 30% of the R1 radicals can be ethyl, propyl or butyl radicals.
  • alkyl radicals with up to 18 carbon atoms can also be bonded to silicon. However, they are usually only in a small proportion up to 10% of the radicals R1.
  • the bridging bivalent Koh hydrogen radical is preferably the -CH2CH2CH2 radical.
  • the radicals R4, R5 bound to nitrogen are preferably alkyl radicals having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isobutyl, cyclohexyl or decyl radicals.
  • the radicals R4, R5 can also be alkyloxyalkyl radicals, for example -CH2CH2OCH3 radicals.
  • a cyclic residue can take the place of two residues.
  • the radicals R4, R5 together form part of a morpholine or piperazine ring, for example to have.
  • R6 is a lower, preferably the methyl radical.
  • R7 is a hydrogen, an acyl radical or the radical R6, preferably the methyl, ethyl, propyl or butyl radical.
  • z has a value from 1 to 10
  • n and m have a value from 1 to 20.
  • indices x and y indicate the number of the difunctional silicon unit.
  • x is 60 to 200 and y is 3 to 10.
  • release agents or additives can also be used in the process according to the invention.
  • These are in particular metal salts of fatty acids with more than 8 carbon atoms, preferably the calcium salts of stearic and palmitic acid, furthermore esters of fatty acids with trihydric or polyhydric alcohols, e.g. Glycerol tristearate, pentaerythritol tetraoleate or sorbitan laurate.
  • auxiliary release agents are expediently added in amounts of 1 to 5% by weight, based on the total weight of the reaction mixture.
  • the compounds to be used in the process according to the invention are prepared in a manner known per se by adding compounds which carry an olefinically unsaturated group instead of the group R 3 to siloxanes having SiH groups, for example in accordance with the reaction:
  • the selected organosilicon compounds should be present in amounts of 0.5 to 10% by weight, based on the total weight of the batch. Amounts of 1 to 5% by weight, in particular 1 to 3% by weight, are preferred.
  • a typical RIM formulation is prepared with a hand mixer. The mixture is placed in a test form and allowed to react there. In otherwise identical tests, internal release agents of the prior art and release agents to be used in the process according to the invention are added. In addition, test foaming is carried out without the addition of a release agent.
  • 100 parts by weight of the polyol component are mixed with 127 parts by weight of the isocyanate component by intensive stirring with a laboratory stirrer at 2500 revolutions in 7 seconds.
  • the still liquid reaction mixture is poured into a closable aluminum mold at a temperature of 60 ° C.
  • a separate lid is used to close the mold and is fastened with screw clamps.
  • the inside of the mold and the inside of the lid used for sealing are provided with a wax-containing release agent before pouring in the reaction mass.
  • the release agent is applied very thinly with a cloth and polished. After a standing time of 4 minutes, the lid of the mold is removed and the tensile forces required are measured with a spring balance.
  • the amount of release agent added was in each case 1.65% by weight, based on the reaction mixture.
  • the measured release force values demonstrate the high effectiveness of the release agents to be used in the method according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

1. Process for the production of polyurethane mouldings by reacting at least one polyol with an organic di- or polyisocyanate in the presence of catalists and release agents with shaping, characterized in that compounds of the general average formula see diagramm : EP0238685,P6,F6 where R**1 is identical or different in the molecule and denotes an alkyl radical having 1 to 18 carbon atoms or an aryl radical, but at least 70% of the R**1 radicals being methyl radicals, R**2 is identical to R**1 or denotes one of the radicals see diagramm : EP0238685,P6,F7 see diagramm : EP0238685,P6,F8 or -R**3 O(C2 H4 O)n (C3 H6 O)m R**7 in which R**3 is a divalent hydrocarbon radical having 2 to 4 carbon atoms, R**4 and R**5 are monovalent hydrocarbon radicals or together are part of a morpholine or piperazine ring, R**6 is a lower alkyl radical having 1 to 4 carbon atoms and R**7 is a hydrogen, acyl or R**6 radical, z is 1 to 10, n is 1 to 20 and m is 1 to 20, with the proviso that, in the average molecule, at least one R**2 radical has the meaning see diagramm : EP0238685,P6,F1 x is 20 to 300 and y is 1 to 20, are used in amounts from 0.5 to 10% by weight, relative to the total weight of the reaction batch, as an internal release agent.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Polyurethan­formteilen durch Umsetzung von mindestens einem Polyol mit einem or­ganischen Di- oder Polyisocyanat in Gegenwart von Katalysatoren und Trennmitteln unter Formgebung.The invention relates to a process for producing molded polyurethane parts by reacting at least one polyol with an organic di- or polyisocyanate in the presence of catalysts and mold release agents with shaping.

Die Erfindung betrifft insbesondere ein Verfahren zur Herstellung von Polyurethanformteilen nach dem Reaction-Injection-Molding (RIM) -Ver­fahren.The invention relates in particular to a process for the production of molded polyurethane parts by the reaction injection molding (RIM) process.

Polyurethanformteile werden in großem Umfang als Karosserieteile, wie Schürzen, Spoiler, Kotflügel, in der Automobilindustrie verwendet. Aufgrund ihrer Zähigkeit und Abriebfestigkeit sind sie als Schuhsoh­len, Absätze und für viele andere Zwecke geeignet.Polyurethane molded parts are widely used as body parts, such as aprons, spoilers, fenders, in the automotive industry. Due to their toughness and abrasion resistance, they are suitable as shoe soles, heels and for many other purposes.

Die Aushärtung der Polyurethane geschieht unter gleichzeitiger Form­gebung in geschlossenen, geheizten Formen. Dabei hat insbesondere das Reaction-Injection-Molding-Verfahren, sogenanntes RIM-Verfahren, be­sondere Bedeutung erlangt.The curing of the polyurethanes takes place with simultaneous shaping in closed, heated molds. The reaction injection molding process, the so-called RIM process, has become particularly important.

Ein erhebliches Problem ergibt sich daraus, daß die geformten Poly­urethanteile dazu neigen, mit der inneren Formwandung zu verkleben. Zwar sind dem mit der Herstellung von Formteilen aus reaktiven Massen vertrauten Fachmann Trennmittel in großer Zahl bekannt. Derartige Trennmittel können auf die Innenwände der Formen aufgebracht oder als interne Trennmittel dem Reaktionsansatz zugegeben werden. Die inter­nen Trennmittel können unterschiedlichen Substanzklassen angehören. Als interne Trennmittel werden Metallseifen, wie z.B. Zinkstearat, Ester höherer Fettsäuren, natürliche oder synthetische Öle, Wachse oder Silicone verwendet.A significant problem arises from the fact that the molded polyurethane parts tend to stick to the inner mold wall. The skilled worker familiar with the production of molded parts from reactive compositions is known in large numbers. Such release agents can be applied to the inner walls of the molds or added to the reaction batch as internal release agents. The internal release agents can belong to different classes of substances. Metal soaps such as zinc stearate are used as internal release agents. Esters of higher fatty acids, natural or synthetic oils, waxes or silicones are used.

Dabei sind als interne Trennmittel insbesondere solche Produkte be­vorzugt, die eine besondere Vorbereitung der Formen überflüssig machen, die Eigenschaften des ausreagierten, geformten Kunststoffes nicht beeinflussen und möglichst keine Änderung der Oberflächeneigen­schaften der Formteile, wie etwa eine Beeinträchtigung der Lackier­barkeit, verursachen. Die internen Trennmittel sollen im Reaktions­ansatz gut verteilbar sein, müssen sich aber, um trennend wirken zu können, an der Oberfläche des Formteiles anreichern.Products which make special preparation of the molds superfluous, do not influence the properties of the fully reacted, molded plastic and, as far as possible, cause no change in the surface properties of the molded parts, such as an impairment of the paintability, are preferred as internal release agents. The internal release agents should be easy to distribute in the reaction mixture, but in order to be able to act as separators, they have to accumulate on the surface of the molded part.

Beispiele von internen Trennmitteln, die insbesondere bei der Her­stellung von Polyurethanformteilen nach dem RIM-Verfahren eingesetzt werden sollen, sind siliciumorganische Blockmischpolymerisate, welche neben Siloxanblöcken Polyoxyalkylenblöcke aufweisen. Dabei spielt offenbar die Struktur der Verbindungen eine für das Trennverhalten wesentliche Rolle.Examples of internal release agents which are to be used in particular in the production of molded polyurethane parts by the RIM process are organosilicon block copolymers which, in addition to siloxane blocks, have polyoxyalkylene blocks. The structure of the connections obviously plays an important role in the separation behavior.

So ist z.B. der DE-OS 25 43 638 zu entnehmen, daß die Verbindungen der Formel

Figure imgb0001
den Verbindungen mit der Formel
Figure imgb0002
Figure imgb0003
 unterlegen sein sollen, wobei in den Formeln II bis V die Indices x jeweils einen Mittelwert von 3 bis 45 haben, der Index y jeweils für einen Mittelwert von 8 bis 198 steht, Me Methyl bedeutet und der Rest (-OR)x für ein Polyoxyalkylenpolymer oder ein Polyoxyalkylencopolymer steht, wobei R aus Ethylenresten oder Butylenresten oder Gemischen aus Ethylen- oder Butylenresten mit Propylenresten zusammengesetzt ist, wobei die Menge aus Ethylen- oder Butylenresten im Verhältnis zur Menge der Propylenreste so gewählt ist, daß das Verhältnis aus den Kohlenstoffatomen zu den Sauerstoffatomen im gesamten Block (-OR-) 2,0 : 1 bis 2,9 : 1 ausmacht.For example, DE-OS 25 43 638 shows that the compounds of the formula
Figure imgb0001
 the compounds with the formula
Figure imgb0002
Figure imgb0003
 should be inferior, where in the formulas II to V the indices x each have an average of 3 to 45, the index y each represents an average of 8 to 198, Me is methyl and the rest (-OR) x is a polyoxyalkylene polymer or a polyoxyalkylene copolymer, where R is composed of ethylene residues or butylene residues or mixtures of ethylene or butylene residues with propylene residues, the amount of ethylene or butylene residues in relation to the amount of propylene residues being chosen such that the ratio of the carbon atoms to the oxygen atoms in the entire block (-OR-) 2.0: 1 to 2.9: 1.

Dieser Offenlegungsschrift können auch Testmethoden zur Ermittlung und zum Vergleich der Trennfähigkeit verschiedener Trennmittel ent­nommen werden.Test methods for determining and comparing the separability of different release agents can also be found in this published specification.

Spätere Arbeiten zeigen, daß gewisse funktionelle Gruppen die Trenn­fähigkeit verbessern können. Siloxane mit solchen funktionellen Gruppen sind aus der US-PS 4 076 695 bekannt. Sie enthalten als funk­tionelle Gruppen an Kohlenwasserstoffgruppen Carboxylgruppen, die ihrerseits mittels einer Si-C- oder SiOC-Bindung mit dem Siloxange­rüst verbunden sind. Diese Trennmittel mit Carboxylgruppen bilden je­doch keine stabilen Mischungen mit den Polyolen, die Amin- und gege­benenfalls Sn-Katalysatoren enthalten. Durch den Zusatz dieser Ver­bindungen wird außerdem die Gelzeit des Polyurethansystems ver­längert.Later work shows that certain functional groups can improve the ability to separate. Siloxanes with such functional groups are known from US Pat. No. 4,076,695. They contain, as functional groups on hydrocarbon groups, carboxyl groups which in turn are connected to the siloxane skeleton by means of an Si-C or SiOC bond. However, these release agents with carboxyl groups do not form stable mixtures with the polyols which contain amine and optionally Sn catalysts. The addition of these compounds also extends the gel time of the polyurethane system.

Eine Verwendung dieser Verbindungen als Bestandteil der Isocyanatkom­ponente ist aufgrund ihrer Reaktivität nicht möglich.The use of these compounds as a component of the isocyanate component is not possible because of their reactivity.

Diese Nachteile wurden zwar bei Verwendung der in der US-PS 4 472 341 beschriebenen siliciumorganischen Verbindungen als interne Trennmit­tel weitgehend überwunden. Diese Siloxane haben Einheiten

Figure imgb0004
wobei R eine niedere Alkyl- oder Arylgruppe ist. R¹ ist ein zweiwer­tiger Kohlenwasserstoffrest, der Sauerstoff- oder Schwefelatome ent­halten kann. R² ist eine niedrige Alkoxy-, eine Aroxygruppe oder die Gruppe R³O(CHR⁴CH₂O-)x , wobei R³ ein Wasserstoffrest oder eine niedere Alkylgruppe, R⁴ ein Wasserstoff- oder Methylrest und x einen Wert von 1 bis 50 hat. Jedoch kann ihr Trennverhalten noch nicht völlig befriedigen. Gleiches gilt für Siloxane mit organisch gebunde­nen CONR₂-Gruppen, wobei R Waserstoffreste bedeutet.These disadvantages have been largely overcome when the organosilicon compounds described in US Pat. No. 4,472,341 are used as internal release agents. These siloxanes have units
Figure imgb0004
 where R is a lower alkyl or aryl group. R¹ is a divalent hydrocarbon residue that may contain oxygen or sulfur atoms. R² is a lower alkoxy, an aroxy group or the group R³O (CHR⁴CH₂O-) x , where R³ is a hydrogen radical or a lower alkyl group, R⁴ is a hydrogen or methyl radical and x has a value from 1 to 50. However, their separation behavior cannot yet be completely satisfactory. The same applies to siloxanes with organically bound CONR₂ groups, where R means residues of hydrogen.

Der Erfindung liegt deshalb die Aufgabe zugrunde, interne Trennmittel zur Herstellung von Polyurethanformteilen, insbesondere nach dem RIM-­Verfahren, zu finden, die die eingangs gezeigten Anforderungen mög­lichst optimal erfüllen.The invention is therefore based on the object of finding internal release agents for the production of molded polyurethane parts, in particular using the RIM process, which optimally meet the requirements shown at the outset.

Überraschenderweise gelingt dies erfindungsgemäß dadurch, daß man als internes Trennmittel Verbindungen der allgemeinen durchschnittlichen Formel

Figure imgb0005
wobei
R¹ im Molekül gleich oder verschieden ist und einen Alkylrest mit 1 bis 18 Kohlenstoffatomen oder einen Arylrest bedeutet, minde­stens 70 % der Reste R¹ aber Methylreste sind,
R² gleich R¹ ist oder einen der Reste
Figure imgb0006
 oder
-R³O(C₂H₄O)n(C₃H₆O)mR⁷ bedeutet, in denen
R³ ein zweiwertiger Kohlenwasserstoffrest mit 2 bis 4 Koh­lenstoffatomen ist,
R⁴, R⁵ einwertige Kohlenwasserstoffreste oder gemeinsam Be­standteil eines Morpholin- oder Piperazinringes sind,
R⁶ ein niederer Alkylrest mit 1 bis 4 Kohlenstoffatomen und
R⁷ ein Wasserstoff-, Acyl- oder der R⁶-Rest ist,
z = 1 bis 10,
n = 1 bis 20 und
m = 1 bis 20 ist,
mit der Maßgabe, daß in durchschnittlichen Molekül mindestens ein Rest R² die Bedeutung
Figure imgb0007
 hat,
x = 20 bis 300 und
y = 1 bis 20 ist,
in Mengen von 0,5 bis 10 Gew.%, bezogen auf Gesamtgewicht des Reak­tionsansatzes, verwendet.Surprisingly, this is achieved according to the invention in that compounds of the general average formula are used as the internal release agent
Figure imgb0005
 in which
R¹ is the same or different in the molecule and represents an alkyl radical with 1 to 18 carbon atoms or an aryl radical, but at least 70% of the radicals R¹ are methyl radicals,
R² is R¹ or one of the radicals
Figure imgb0006
 or
-R³O (C₂H₄O) n (C₃H₆O) m R⁷ means in which
R³ is a divalent hydrocarbon radical with 2 to 4 carbon atoms,
R⁴, R⁵ are monovalent hydrocarbon radicals or together form part of a morpholine or piperazine ring,
R⁶ is a lower alkyl radical with 1 to 4 carbon atoms and
R⁷ is a hydrogen, acyl or the R⁶ radical,
z = 1 to 10,
n = 1 to 20 and
m = 1 to 20,
with the proviso that in average molecule at least one radical R² has the meaning
Figure imgb0007
 Has,
x = 20 to 300 and
y = 1 to 20,
in amounts of 0.5 to 10% by weight, based on the total weight of the reaction mixture.

Der Rest R¹ ist an Silicium gebunden und vorzugsweise ein niederer Alkylrest mit 1 bis 4 Kohlenstoffatomen, besonders bevorzugt der Me­thylrest. Die Bedeutung des Restes R¹ kann im durchschnittlichen Mo­lekül unterschiedlich sein, jedoch muß die Bedingung erfüllt sein, daß mindestens 70 % der Reste R¹ Methylreste sind. Die übrigen 30 % der Reste R¹ können Ethyl-, Propyl- oder Butylreste sein. Es können jedoch auch Alkylreste mit bis zu 18 Kohlenstoffatomen an Silicium gebunden sein. Sie sind jedoch in der Regel nur in geringem Anteil bis zu 10 % der Reste R¹ enthalten.The radical R 1 is bonded to silicon and is preferably a lower alkyl radical having 1 to 4 carbon atoms, particularly preferably the methyl radical. The meaning of the radical R¹ can vary in the average molecule, but the condition must be fulfilled that at least 70% of the radicals R¹ are methyl radicals. The remaining 30% of the R¹ radicals can be ethyl, propyl or butyl radicals. However, alkyl radicals with up to 18 carbon atoms can also be bonded to silicon. However, they are usually only in a small proportion up to 10% of the radicals R¹.

Mindestens ein Rest R² muß im mittleren Molekül die Bedeutung des Restes

Figure imgb0008
haben. Der verbrückende zweiwertige Koh­ lenwasserstoffrest ist vorzugsweise der -CH₂CH₂CH₂-Rest. Die am Stickstoff gebundenen Reste R⁴, R⁵ sind vorzugsweise Alkylreste mit 1 bis 10 Kohlenstoffatomen, wie Methyl-, Ethyl-, Propyl-, Isobutyl-, Cyclohexyl- oder Decylreste. Die Reste R⁴, R⁵ können auch Alkyloxy­alkylreste, z.B. -CH₂CH₂OCH₃-Reste, sein. An die Stelle zweier Reste kann ein cyclischer Rest treten. Dabei sind die Reste R⁴, R⁵ gemein­sam Bestandteil eines Morpholin- oder Piperazinringes, z.B.
Figure imgb0009
 haben. Dabei ist R⁶ ein niederer, vorzugsweise der Methyl­rest. R⁷ ist ein Wasserstoff-, ein Acylrest oder der Rest R⁶, vor­zugsweise der Methyl-, Ethyl-, Propyl- oder Butylrest. z hat einen Wert von 1 bis 10, n und m einen Wert von jeweils 1 bis 20. Diese Reste R⁴ tragen zur Verträglichkeit der siliciumorganischen Verbin­dungen mit dem Verschäumungspolyol bei.At least one R² residue in the middle molecule must have the meaning of the rest
Figure imgb0008
 to have. The bridging bivalent Koh hydrogen radical is preferably the -CH₂CH₂CH₂ radical. The radicals R⁴, R⁵ bound to nitrogen are preferably alkyl radicals having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isobutyl, cyclohexyl or decyl radicals. The radicals R⁴, R⁵ can also be alkyloxyalkyl radicals, for example -CH₂CH₂OCH₃ radicals. A cyclic residue can take the place of two residues. The radicals R⁴, R⁵ together form part of a morpholine or piperazine ring, for example
Figure imgb0009
 to have. R⁶ is a lower, preferably the methyl radical. R⁷ is a hydrogen, an acyl radical or the radical R⁶, preferably the methyl, ethyl, propyl or butyl radical. z has a value from 1 to 10, n and m have a value from 1 to 20. These Residues R⁴ contribute to the compatibility of the organosilicon compounds with the foaming polyol.

Die Indices x und y kennzeichnen die Anzahl der difunktionellen Sili­ciumeinheit. Vorzugsweise ist x gleich 60 bis 200 und y gleich 3 bis 10.The indices x and y indicate the number of the difunctional silicon unit. Preferably x is 60 to 200 and y is 3 to 10.

Es besteht Grund zu der Vermutung, daß die hohe Wirksamkeit der beim erfindungsgemäßen Verfahren zu verwendenden Trennmittel in der Anwe­senheit eines tertiären Stickstoffatoms in den Verbindungen der Formel I zu suchen ist. Hierdurch wird möglicherweise die Aushärtung der Polyurethanformteile im Oberflächenbereich zusätzlich kataly­siert.There is reason to suspect that the high effectiveness of the release agents to be used in the process according to the invention is to be sought in the presence of a tertiary nitrogen atom in the compounds of the formula I. This may additionally catalyze the curing of the molded polyurethane parts in the surface area.

Außer diesen speziellen siliciumorganischen Verbindungen können beim erfindungsgemäßen Verfahren auch an sich bekannte Trenn- oder Zusatz­mittel mit eingesetzt werden. Dies sind insbesondere Metallsalze von Fettsäuren mit mehr als 8 Kohlenstoffatomen, vorzugsweise die Cal­ciumsalze der Stearin- und Palmitinsäure, ferner Ester von Fettsäuren mit drei- oder mehrwertigen Alkoholen, wie z.B. Glycerintristearat, Pentaerythrittetraoleat oder Sorbitanlaurat. Diese Hilfstrennmittel werden zweckmäßig in Mengen von 1 bis 5 Gew.-%, bezogen auf Gesamtge­wicht des Reaktionsansatzes, zugegeben.In addition to these special organosilicon compounds, known release agents or additives can also be used in the process according to the invention. These are in particular metal salts of fatty acids with more than 8 carbon atoms, preferably the calcium salts of stearic and palmitic acid, furthermore esters of fatty acids with trihydric or polyhydric alcohols, e.g. Glycerol tristearate, pentaerythritol tetraoleate or sorbitan laurate. These auxiliary release agents are expediently added in amounts of 1 to 5% by weight, based on the total weight of the reaction mixture.

Die Herstellung der beim erfindungsgemäßen Verfahren zu verwendenden Verbindungen gelingt in an sich bekannter Weise durch Addition von Verbindungen, die statt der Gruppe R³ eine olefinisch ungesättigte Gruppe tragen, an Siloxane mit SiH-Gruppen, z.B. entsprechend der Reaktion:

Figure imgb0010
The compounds to be used in the process according to the invention are prepared in a manner known per se by adding compounds which carry an olefinically unsaturated group instead of the group R 3 to siloxanes having SiH groups, for example in accordance with the reaction:
Figure imgb0010

In ähnlicher Weise reagieren die Verbindungen

Figure imgb0011
und
CH₂=CHCH₂O(C₂H₄O)n(C₃H₆O)mR⁷
zur Einführung der zusätzlich genannten Reste R². Die Reaktion wird durch Zusatz von Platinverbidungen katalysiert.The connections react in a similar way
Figure imgb0011
 and
CH₂ = CHCH₂O (C₂H₄O) n (C₃H₆O) m R⁷
to introduce the additionally mentioned residues R². The reaction is catalyzed by the addition of platinum compounds.

Eine bevorzugte Reaktionsdurchführung besteht darin, daß zunächst ein SiH-funktionelles Polysiloxan gemäß obiger Formel mit Allylglycid­ether gegebenenfalls in Mischung mit CH₂=CH-CH₂-O(C₂H₄O)n(C₃H₆O)mR⁷ in Gegenwart von Platinverbindungen, wie z.B. H₂PtCl₆ . 6 H₂O, umge­setzt wird und danach die eingeführten Epoxidreste mit Verbindungen der allgemeinen Formel

Figure imgb0012
oder HO(C₂H₄O)zOR⁶ in an sich be­kannter Weise umgesetzt werden.A preferred reaction procedure is that first a SiH-functional polysiloxane according to the above formula with allyl glycidyl ether, optionally in a mixture with CH₂ = CH-CH₂-O (C₂H₄O) n (C₃H₆O) m R⁷ in the presence of platinum compounds such as H₂PtCl₆. 6 H₂O, is implemented and then the introduced epoxy radicals with compounds of the general formula
Figure imgb0012
 or HO (C₂H₄O) z OR⁶ are implemented in a manner known per se.

Weitere Syntheseangaben können der DE-PS 32 15 317, Angaben zur Kata­lyse der DE-PS 31 33 869 entnommen werden.Further synthesis information can be found in DE-PS 32 15 317, information on catalysis in DE-PS 31 33 869.

Bei dem erfindungsgemäßen Verfahren sollen die ausgewählten silicium­organischen Verbindungen in Mengen von 0,5 bis 10 Gew.-%, bezogen auf Gesamtgewicht des Ansatzes, enthalten sein. Bevorzugt sind Mengen von 1 bis 5 Gew.-%, insbesondere 1 bis 3 Gew.-%.In the process according to the invention, the selected organosilicon compounds should be present in amounts of 0.5 to 10% by weight, based on the total weight of the batch. Amounts of 1 to 5% by weight, in particular 1 to 3% by weight, are preferred.

In den folgenden Beispielen wird die gegenüber des Standes der Technik verbesserte Trennkraft der beim erfindungsgemäßen Verfah­ren zu verwendenden Verbindungen näher gezeigt.In the following examples, the separation force of the compounds to be used in the process according to the invention, which is improved compared to the prior art, is shown in more detail.

Hierzu wird ein typische RIM-Formulierung mit einem Handmischgerät zubereitet. Man gibt das Gemisch in eine Testform und läßt es dort reagieren. Bei jeweils sonst identischen Versuchen werden interne Trennmittel des Standes der Technik und beim erfindungsgemäßen Ver­fahren zu verwendende Trennmittel zugesetzt. Zusätzlich wird eine Testverschäumung ohne Trennmittelzusatz durchgeführt.For this purpose, a typical RIM formulation is prepared with a hand mixer. The mixture is placed in a test form and allowed to react there. In otherwise identical tests, internal release agents of the prior art and release agents to be used in the process according to the invention are added. In addition, test foaming is carried out without the addition of a release agent.

Versuchsdurchführung:Carrying out the experiment:

100 Gew.-Teile eines Polyetherpolyols mit der OH-Zahl 27, das durch Anlagerung von Propylenoxid an Trimethylolpropan und anschließendes Anlagern von ethylenoxid hergestellt worden war, werden mit 28 Gew.-­Teilen Ethylenglykol, 0,35 Gew.-Teilen Triethylendiamin, 0,02 Gew.-­Teilen Dibutylzinndilaurat und 5 Gew.-Teilen des Trennmittels ge­mischt (Polyolkomponente).100 parts by weight of a polyether polyol with the OH number 27, which had been prepared by addition of propylene oxide to trimethylolpropane and subsequent addition of ethylene oxide, are mixed with 28 parts by weight of ethylene glycol, 0.35 parts by weight of triethylenediamine, 02 parts by weight of dibutyltin dilaurate and 5 parts by weight of the release agent mixed (polyol component).

Als Isocyanat wird ein durch Umsetzung von 4,4ʹ-Diisocyanatodiphenyl­methan mit Tripropylenglykol erhaltenes Produkt, NCO-Gehalt 23 %, verwendet (Isocyanatkomponente).A product obtained by reacting 4,4'-diisocyanatodiphenylmethane with tripropylene glycol, NCO content 23%, is used as isocyanate (isocyanate component).

Jeweils 100 Gew.-Teile der Polyolkomponente werden mit 127 Gew.-Tei­len der Isocyanatkomponente durch intensives Rühren mit einem Labor­rührer mit 2500 Umdrehungen in 7 Sekunden vermischt. Das noch flüssig vorliegende Reaktionsgemisch wird in eine auf 60°C temperierte ver­schließbare Aluminiumform gegossen. Zum Verschließen der Form dient ein separater Deckel, der mit Schraubzwingen befestigt wird. Die Forminnenflächen und die Innenseite des zum Verschließen verwendeten Deckels werden vor dem Eingießen der Reaktionsmasse mit einem wachs­haltigen Trennmittel versehen. Dazu wird das Trennmittel mit einem Lappen sehr dünn aufgetragen und poliert. Nach einer Standzeit von 4 Minuten wird der Deckel der Form entfernt und die dabei notwendigen Zugkräfte mit einer Federwaage gemessen. Ohne Verwendung eines inter­nen Trennmittels verklebt der Deckel mit dem Reaktionsgut, so daß dbeim gewaltsamen Entfernen des Deckels die Oberfläche des Formlings beschädigt wird und Teile des Reaktionsgutes auf der Deckelinnenseite haften. Bei Verwendung interner Trennmittel wird die Entfernung des Formdeckels wesentlich erleichtert und eine Beschädigung der Ober­fläche des Formlings vermieden. Die Ergebnisse von Vergleichsversu­chen sind in der folgenden Tabelle zusammengestellt. Als erfindungs­gemäß zu verwendende siliciumorganische Polymerisate wurden einge­setzt:

Figure imgb0013
Verbindung A R* = Morpholinrest
Verbindung B R* = N-Monomethylcyclohexylaminrest
Verbindung C R* = Di-(2-methoxyethyl)aminrest
Verbindung D R* = N-Methylpiperazinrest100 parts by weight of the polyol component are mixed with 127 parts by weight of the isocyanate component by intensive stirring with a laboratory stirrer at 2500 revolutions in 7 seconds. The still liquid reaction mixture is poured into a closable aluminum mold at a temperature of 60 ° C. A separate lid is used to close the mold and is fastened with screw clamps. The The inside of the mold and the inside of the lid used for sealing are provided with a wax-containing release agent before pouring in the reaction mass. For this purpose, the release agent is applied very thinly with a cloth and polished. After a standing time of 4 minutes, the lid of the mold is removed and the tensile forces required are measured with a spring balance. Without using an internal release agent, the lid sticks to the reaction product, so that when the cover is removed by force, the surface of the molded article is damaged and parts of the reaction product adhere to the inside of the cover. When using internal release agents, the removal of the mold cover is made considerably easier and damage to the surface of the molding is avoided. The results of comparative tests are summarized in the following table. Organosilicon polymers to be used according to the invention were:
Figure imgb0013
 Compound AR * = morpholine residue
Compound BR * = N-monomethylcyclohexylamine residue
Compound CR * = di- (2-methoxyethyl) amine residue
Compound DR * = N-methylpiperazine residue

Als Vergleichssubstanzen wurden verwendet
Verbindung E beschrieben in US-PS 4 076 695, Beispiel 1
Verbindung F beschrieben in DE-OS 25 43 638, Seite 20 oben
Verbindung G beschrieben in US-PS 4 472 341 m = 80, q = 3, R = CH₃, n = 2, nʹ = 1, R² = -OCH₃The following were used as reference substances
Compound E described in U.S. Patent 4,076,695, Example 1
Compound F described in DE-OS 25 43 638, page 20 above
Compound G described in U.S. Patent 4,472,341 m = 80, q = 3, R = CH₃, n = 2, nʹ = 1, R² = -OCH₃

Die zugesetzte Menge Trennmittel betrug jeweils 1,65 Gew.-%, bezogen auf Reaktionsansatz.

Figure imgb0014
The amount of release agent added was in each case 1.65% by weight, based on the reaction mixture.
Figure imgb0014

Die gemessenen Trennkraftwerte belegen die hohe Wirksamkeit der beim erfindungsgemäßen Verfahren zu verwendenden Trennmittel.The measured release force values demonstrate the high effectiveness of the release agents to be used in the method according to the invention.

Claims (3)

Verfahren zur Herstellung von Polyurethanformteilen durch Umset­zung von mindestens einem Polyol mit einem organischen Di- oder Polyisocyanat in Gegenwart von Katalysatoren und Trennmitteln unter Formgebung, dadurch gekennzeichnet, daß man als internes Trennmittel Verbindungen der allgemeinen durchschnittlichen Formel
Figure imgb0015
 wobei
R¹ im Molekül gleich oder verschieden ist und einen Alkylrest mit 1 bis 18 Kohlenstoffatomen oder einen Arylrest bedeutet, minde­stens 70 % der Reste R¹ aber Methylreste sind,
R² gleich R¹ ist oder einen der Reste
Figure imgb0016
 oder
-R³O(C₂H₄O)n(C₃H₆O)mR⁷ bedeutet, in denen
R³ ein zweiwertiger Kohlenwasserstoffrest mit 2 bis 4 Koh­lenstoffatomen ist,
R⁴, R⁵ einwertige Kohlenwasserstoffreste oder gemeinsam Be­standteil eines Morpholin- oder Piperazinringes sind,
R⁶ ein niederer Alkylrest mit 1 bis 4 Kohlenstoffatomen und
R⁷ ein Wasserstoff-, Acyl- oder R⁶-Rest ist,
z = 1 bis 10,
n = 1 bis 20 und
m = 1 bis 20 ist,
mit der Maßgabe, daß in durchschnittlichen Molekül mindestens ein Rest R² die Bedeutung
Figure imgb0017
 hat,
x = 20 bis 300 und
y = 1 bis 20 ist,
in Mengen von 0,5 bis 10 Gew.%, bezogen auf Gesamtgewicht des Reaktionsansatzes, verwendet.Process for the production of molded polyurethane parts by reacting at least one polyol with an organic di- or polyisocyanate in the presence of catalysts and mold release agents, with shaping, characterized in that compounds of the general average formula are used as the internal mold release agent
Figure imgb0015
 in which
R1 in the molecule is the same or different and denotes an alkyl radical with 1 to 18 carbon atoms or an aryl radical, but at least 70% of the radicals R1 are methyl radicals,
R² is R¹ or one of the radicals
Figure imgb0016
 or
-R³O (C₂H₄O) n (C₃H₆O) m R⁷ means in which
R³ is a divalent hydrocarbon radical with 2 to 4 carbon atoms,
R⁴, R⁵ are monovalent hydrocarbon radicals or together form part of a morpholine or piperazine ring,
R⁶ is a lower alkyl radical with 1 to 4 carbon atoms and
R⁷ is a hydrogen, acyl or R⁶ radical,
z = 1 to 10,
n = 1 to 20 and
m = 1 to 20,
with the proviso that in average molecule at least a residue R² the meaning
Figure imgb0017
 Has,
x = 20 to 300 and
y = 1 to 20,
in amounts of 0.5 to 10% by weight, based on the total weight of the reaction mixture. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Verbin­dungen der vorgenannten Formel verwendet, welche eine oder mehrere der bevorzugten Bedingungen
R¹ = Methylrest,
R³ = -CH₂CH₂-CH₂-Rest,
R⁴, R⁵ = Alkylrest mit 1 bis 10 Kohlenstoffatomen, wobei die Kohlenstoffkette durch ein Sauerstoffatom unter­brochen sein kann oder gemeinsam der
Figure imgb0018
 wobei R⁸ ein Alkylrest oder ein Alkyloxyalkylrest mit bis zu 10 Kohlenstoffatomen ist,
x = 60 bis 200,
y = 3 bis 10,
erfüllt.2. The method according to claim 1, characterized in that one uses compounds of the aforementioned formula which one or more of the preferred conditions
R¹ = methyl radical,
R³ = -CH₂CH₂-CH₂ residue,
R⁴, R⁵ = alkyl radical with 1 to 10 carbon atoms, where the carbon chain can be interrupted by an oxygen atom or together the
Figure imgb0018
 where R⁸ is an alkyl radical or an alkyloxyalkyl radical having up to 10 carbon atoms,
x = 60 to 200,
y = 3 to 10,
Fulfills. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man dem Reaktionsansatz zusätzlich Metallsalze von Fettsäuren mit mehr als 8 Kohlenstoffatomen oder Ester dieser Fettsäuren mit drei- oder mehrwertigen Alkoholen in Mengen von 1 bis 5 %, bezogen auf Gesamtwicht des Reaktionsansatzes, zugibt.3. The method according to claim 1 or 2, characterized in that the reaction mixture additionally metal salts of fatty acids with more than 8 carbon atoms or esters of these fatty acids with trihydric or polyhydric alcohols in amounts of 1 to 5%, based on the total weight of the reaction mixture .
EP86104125A 1985-03-19 1986-03-25 Process for the production of moulded polyurethane parts Expired EP0238685B1 (en)

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Cited By (5)

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EP0277816A1 (en) * 1987-02-04 1988-08-10 Chisso Corporation A polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same
EP0479436A2 (en) * 1990-10-03 1992-04-08 Imperial Chemical Industries Plc Isocyanote reactive blends for internal mould release compositions
EP1275672A1 (en) * 2001-06-27 2003-01-15 National Starch and Chemical Investment Holding Corporation Method for manufacturing amphoteric urethane resin and amphoteric urethane resin and resin composition obtained therewith
DE102014204937A1 (en) 2014-03-17 2015-09-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of a polyurethane molding
DE102015208729A1 (en) 2015-05-11 2016-11-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polyurethane surface prepared for a coating process and process for its preparation

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DE3509810C1 (en) * 1985-03-19 1986-05-15 Th. Goldschmidt Ag, 4300 Essen Process for the production of polyurethane mouldings
US4689383A (en) * 1986-03-18 1987-08-25 Thoratec Laboratories Corp. Hydroxyl-functional disiloxanes and polysiloxane oligomers
DE4023702B4 (en) * 1990-07-26 2007-01-11 Sonderhoff Gmbh Use of a thermosetting one-component polyurethane composition as pourable and sprayable sealant for the production of inflatable rubber-like seals

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EP0083733A1 (en) * 1981-12-15 1983-07-20 Bayer Ag Use of polyisocyanate addition products as mould lacquers and their use as mould release agents for mould lacquers in the production of moulded plastics with a lacquer coating
EP0122743A2 (en) * 1983-04-13 1984-10-24 Ici Americas Inc. Liquid organic polyisocyanate composition for use in reaction injection molding in presence of siloxane mold release agent
EP0133454A1 (en) * 1983-07-05 1985-02-27 The Dow Chemical Company Derivatives of carboxysiloxanes and their use as internal mold release agents
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EP0122743A2 (en) * 1983-04-13 1984-10-24 Ici Americas Inc. Liquid organic polyisocyanate composition for use in reaction injection molding in presence of siloxane mold release agent
EP0133454A1 (en) * 1983-07-05 1985-02-27 The Dow Chemical Company Derivatives of carboxysiloxanes and their use as internal mold release agents
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
EP0277816A1 (en) * 1987-02-04 1988-08-10 Chisso Corporation A polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same
EP0479436A2 (en) * 1990-10-03 1992-04-08 Imperial Chemical Industries Plc Isocyanote reactive blends for internal mould release compositions
EP0479436A3 (en) * 1990-10-03 1992-08-12 Imperial Chemical Industries Plc Isocyanote reactive blends for internal mould release compositions
EP1275672A1 (en) * 2001-06-27 2003-01-15 National Starch and Chemical Investment Holding Corporation Method for manufacturing amphoteric urethane resin and amphoteric urethane resin and resin composition obtained therewith
DE102014204937A1 (en) 2014-03-17 2015-09-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of a polyurethane molding
WO2015140147A1 (en) * 2014-03-17 2015-09-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing a polyurethane moulded part
DE102015208729A1 (en) 2015-05-11 2016-11-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polyurethane surface prepared for a coating process and process for its preparation
DE102015208729B4 (en) 2015-05-11 2021-07-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polyurethane surface prepared for a coating process, process for its production, layer composite and use of an additive

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